Manufacture of calcium hypochlorite



Patented une 1929.

UNITED STATES.

I, I 1,718,284 PATENT "OFFICE.

ANTHONY GEORGE AND MAURICE C. TAYLOR, OF NIAGARA FALLS, NEW YORK, AS-

SIGN ORS TO THE MATHIESON ALKALI WORKS, INC., OF NEW YORK, N. Y., A CORPO- RATION or VIRGINIA.

J MANUFAQTURE or on I No Drawing This invention-relates to improvements in the production of calcium hypochlorite products. The product of this invention comprises calcium hypochlorite associat ed with some sodium chloride. Calciumhypochlorite, that is Ca 0C1) pin pure form is. relatively stable but-ca cium chloride if present in substantial amount makes it relatively unstable. This is apparently. due to the hygroscopic properties of calcium chloride Sodium chloride, on

the contrary, does'not decrease the stability of calcium hypochlorite. This invention .provides an improved method of making calcium hypochlorite products of high purity, particularly with reference to contamination with calcium chloride, and which has several further importantadvantages.

According to the present invention, lime is chlorinated in the presence of caustic soda or sodium hypochlorite in a slurry made up of the lime, the caustic soda or the sodium hypochlorite, and a solution saturated with respect to both sodium chloride and calcium hypochlorite; Such solutions saturatedwith respect to both sodium chloride, or alkali metal chlorides, and calcium hypochlorite will hereinafter be designated as eutectic solutions of these compounds. The invention may be carried out in a variety of ways with the production of various products differing among themselves but all comprising calcium hypochlorite associated with somesodium chloride and substantially free from calcium chloride, or nearly so.

In one way pf carrying out the invention, lime and caustic soda are subjected to chlorinatlon in an eutectic solutionof sodium chloride and calcium hypochlorite. Such an eutectic solution may be prepared, for examto water until no more of either will dissolve. After the addition of sodium hydroxide and lime, for, example in the ratio 0 two moles of the former to one mole of the lat er,,the mixture is chlorinated, advantageously until not more than about 1% of free alkali remains. Crystallization oi the calcium hypochlorite product may be promoted, for example, by agitation, and the product separated, for example, by-filtration, when crystallization is complete. Thefiltrate from which the roduct as been separated may be employe as a mediumin which successive ch'lorinations are carried out.

Application filed August {1, 1926. Serial No. 127,169.

ple, by adding salt and calcium hypochorite LCIUM 'nIzPocHLonI'rE.

ThlS mode of carr ng out the invention is illustrated by the follbwing example: 4.7 lbs., of caustic soda and 4.6 lbs. of high grade lime (95% Ca(OH) are added to 100 lbs. of an eutectic solution containing approximately 19.6 lbs. ofsodium chloride, 9.6 lbs. of calcium hypochlorite and 70.8 lbs. of water. This mixture is chlorinated until less than 1% of free alkali remains in solution, about 8.2 lbs. of chlorine being required. Following ch10 rination, the slurry is stirred for about 1 hr.,

G and the precipitate may then be separated in.

any convenient or desired manner. The precipitated product, may for example, be filtered, or filtered and pressed, or subjected to a combined filtering and pressing operation. The amount of mother liquor remaining in the separated product depends upon the manner in which the precipitate is separated and treated. By filtration without pressing, a product comprising approximately 48%of calcium hypochlorite, 2% or less of calcium chloride, 45% of sodium chloride and 5% .of lime may be obtained." The product can-be dried, for example, in an atmospheric or a vacuum drier at temperatures between 40 and 60 C. After the addition of further quantities of caustic soda and lime, the solution from'which the product is separated may be returned to the chlorination operation. For the maintenance of constant conditions, it is necessary where the separated solution is so returned to replace water removed with the separated hypochlorite product.

'advantageous to maintain a temperature in I theneighborhood of 15 to 30 C. when chlorination is begun and toreduee this to approximately 10 to 15 C. as the chlorination operation is concluded.

In another way of carrying out the invention, the foregoing procedure may be. somewhat modified to effect a reduction in the amount of sodium chloride present in the product. When caustic soda and lime are chlorinated in an eutectic solution as described above, the sodium chloride formed precipitates practicallyat once whereas the calcium hypochlorite tends to remain in solution inan unstable condition. According to the present invention, a part of the salt which settles readily may thus be separated from the hypochlorite product tv removing salt precipitated before precipitation of calcium hypochlorite begins. Immediate precipitacrystallization and precipitation of calcium hypochlorite may be promoted, for example by seeding with crystals of calcium hypochlorite or by an agitation.

This mode of carrying out the. invention is illustrated by the following example: 3.4 lbs. of lime (95% Ca(OH) and 3.49 lbs. of caustic soda are added to 100 lbs. of an eutectic solution containing about 19.6 lbs. of sodium chloride and 9.6 lbs. of calcium hypochlorite and this mixture is chlorinated until not more than about 1% of free alkali remains. The slurry remains thin and in a condition in which chlorination is easily effected without violent agitation substantially to completion. Following chlorination, salt is allowed to set tle for about 10 minutes and the comparatively clear solution then decanted. Crystallization of the hypochlorite product from the decanted solution is then promoted, for example, by stirring or by seeding or by'both. The thick slurry resulting from the crystallization operation may be filtered for the separation of the hypochlorite product and the filtrate so obtained employed as the medium for suc- 'cessive chlorination. The precipitated and separated product may be dried either before or after pressing, and then consists essentially of calcium hypochlorite contami nated only with that salt present in mother liquor remaining on the filter or press cake.

In another way if carrying out the invention, sodium hypoc lorite and lime are together subjected to chlorination in an eutectic solution of sodium chloride and calcium hypochlorite. Instead of employing sodium hypochlorite, a solution of salt and sodium hypochlorite may be prepared by chlorination of a solution of caustic soda and this solution may be used as a source of sodium hypochlorite making due allowance for the salt which 1t contains. Such a sodium hypochlorite solution, or sodium hypochlorite, and lime may be added to an eutectic solution" of salt and calcium hypochlorite and the mixture is chlorinated in much the same manner that caustic soda and lime are subjected to chlorination in such an eutectic solution in the modification of the invention first described. The hy-.

pqihlorite product, however, will contain less sa- This mode of carrying-out the invention Wlll be illustrated by the following example as the medium in which a successive chlorina-' tion of caustic soda is carried out. The sodium hypochlorite solution may, for example, comprise about 29.0 of sodium hypochlorite, 7.5% of sodium chloride, 1.5% of sodium hydroxide and 62.0% of water. 100 lbs. of this sodium hypochlorite solution and 33 lbs. of lime(95% Ca(OH) are added to an amount of an eutectic solution of salt and calcium hypochlorite such that the slurry resulting from chlorination is conveniently handled, and the mixture is chlorinated until less than about 1%of free alkali remains, about 32.6

'lbs. 'of chlorine being required. The precipitated hypochlorite product may be separated in any convenient manner, such as those described above. The product may, for example, be filtered and not pressed, or it may be ltered and pressed, the pressing advantageously being carried to a point only sufficient to maintain the quality of product desired to avoid accumulation of the eutectic solution.

Following the chlorination of sodium hypochlorite and lime in an eutectic solution of salt and calcium hypochlorite, salt may be separated before the precipitation of calcium hypochlorite begins in the manner described in connection with the second foregoing modification of the invention. 1

One of the advantages of the invention is that it is particularly adapted to being carried as. a continuous operation. In continuous operation of the modification ofthe invention first described, for example, the eutectic solution of salt and calcium hypochlorite may be circulated continuously through a receptacle into which lime, caustic soda and chlorine are continuously introduced' inappropriate proportions, and the liquor containing the reaction products circulated to and through a precipitation-and settling tank or tower, from the top of whichtreatment of the separated hypochlorite productmay also be returned in a continuous manner to the receptacle in which the chlorina-' tion is effected. If the precipitated hypochlo rite product is to be separated by settling or some similar operation, it is advantageous to.

maintain the cp ncentration df solids relative- 1y low,"for example less thanabout 10%, but

the entire circulating stream of eutectic soluample by decantation. to the cycle just de-,

tion can be subjected to continuous filtration and the amount of the eutecticsolution necessarv to e maintained in clrculatlon thus decreased by carrying the concentration of solids to a higher value. It is also necessary, in

such continuous operation, to add water suificient to maintain a constant volume of circu scribed. The third and fourth modifications of the invention described above may also be "carried out continuously in a manner similar to that described in connection with the first and second modifications of the invention.

' While theinvention has heen described with particular reference to the use ofsodium hydroxide, sodium hypochlorite and sodium chloride, similar compounds of other alkali metals are also useful in carrying out the invention. When used. the product will then comprise calcium '.hypochlorite associated with the chloride of such other alkah metal. The alkali metal compounds useful in connection with the chlorination of lime in carrying out the invention include those which in the presence of lime and chlorine react to form calcium hypochlorite and the alkali metal chloride.

We claim:

1. An improved method of making a hypo chlorite product which comprises chlorinatlng a slurry containing lime and an alkali metal compound. reacting to form calcium hypochlorite, and an alkali metal chloride in the presence of lime and chlorine, in an eutectic solution of calcium hypochlorite and the chloride of the alkali metal.

2. improved method of making a hypochlorite product'which comprises chlorinatmg a slurrycontaining lime and a sodium compound, reacting to form calcium hypochlorlte and. sodium chloride in the presence of limeand chlorine, m an eutectic solution of calcium hypochlorite and sodium chloride.

3 An improved method of making a hypochlorite product which comprises chlorinat ing a slurry containing lime and sodium hypochlorite in an eutectic solution of'calcium hypochlorite and sodium chloride.

4. An improved method of makin chlorite product which comprises chlorinating a slurry containing lime and a solution of sodium hypochlorite in an eutectic solution of calcium hypochlorite and sodium chloride. i

5. An improved method of making a hypochlorite product which comprises chlorinating a slurry containing-lime and a solution of sodium hypochlorite and sodium chloride.

in an eutectic solution of calcium hypochlorite and sodium chloride.

6. An improved method of making a hypochlorite product which comprises chlorinating a solution of caustic soda, adding this chlorinated solution together with lime to an eutectic solution of calcium hypochlorite and sodium chloride, and chlorinating the resulting mixture.

7. An improved method of making a hypochlorite product which comprises chlorinat ing a slurry containing lime and a sodium compound, reacting to form calicum hypochlorite and sodium chloride in the presence of lime and chlorine, in an eutectic'solut-ion of calcium hypochlorite and sodium chloride, and separating precipitated sodium chloride before calcium hypochlorite begins to precipitate.

8; An improved method of making a hypo chlorite productwhich comprises bringing an eutectic solution of sodium chloride and calcium hypochlorite to supersaturation with In testimony whereof we affix oursigna tures. 1

ANTHONY GEORGE. MAURICE o. TAYLOR. 

